Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS4457944 A
Publication typeGrant
Application numberUS 06/332,950
Publication dateJul 3, 1984
Filing dateDec 21, 1981
Priority dateAug 21, 1981
Fee statusPaid
Also published asDE3133078A1, EP0072988A1, EP0072988B1
Publication number06332950, 332950, US 4457944 A, US 4457944A, US-A-4457944, US4457944 A, US4457944A
InventorsJens Conrad, Ulf-Armin Schaper, Ulrich Zeidler
Original AssigneeHenkel Kommanditgesellschaft Auf Aktien
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
1,3-Dialkyl-cyclohexanes, method of production and method of use in cosmetics
US 4457944 A
Abstract
A 1,3-dialkyl-cyclohexane having the formula: ##STR1## wherein R1 is a member selected from the group consisting of hydrogen and straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl; as well as a method of production and its use in cosmetic preparations.
Images(5)
Previous page
Next page
Claims(4)
We claim:
1. In a cosmetic preparation selected from the group consisting of suspensions, gels, emulsions, ointments and pastes comprising cosmetic adjuvants selected from the group consisting of water, preservatives, sequestering agents, perfumes, solvents, opacifiers, thickeners, dyes, pH-modifying additives, plant extracts, and skin care ingredients selected from the group consisting of collagens, fatty acids, fatty acid esters, glycols, glycol ethers, animal oils, plant oils and synthetic oils, wherein the improvement comprises, as a refatting cosmetic oil, from 2% to 25% by weight of at least one 1,3-dialkyl-cyclohexane of the formula ##STR13## wherein R1 is a member selected from the group consisting of hydrogen and a straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl.
2. The cosmetic preparation of claim 1 wherein said amount of said at least one 1,3-dialkyl-cyclohexane in said preparation is from 3% to 25% by weight based on the total weight of said cosmetic product.
3. The cosmetic preparation of claim 1 wherein in said at least one 1,3-dialkyl-cyclohexane, R1 and R2 both represent straight chained or branched C1 -C6 -alkyl.
4. The cosmetic preparation of claim 1 wherein said at least one 1,3-dialkyl-cyclohexane is 1,3-di(2-ethylhexyl)-cyclohexane.
Description
BACKGROUND OF THE INVENTION

The present invention relates to 1,3-dialkylcyclohexanes having the Formula I: ##STR2## wherein R1 is hydrogen or straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl; their production from the correspondingly substituted cyclohexanol or cyclohexanone compounds, and their use as a cosmetic oil, as well as products containing these compounds for the care and treatment of the face, body or hair style.

2,6-Dialkyl-cyclohexanols and methods for their production have been described, Schaper, Fette, Seifen Anstrichmittel (1980), 82, pages 454-456. With this point of departure, the previously unknown 1,3-dialkyl cyclohexane compounds were produced, and it was found, surprisingly, that these constitute especially good cosmetic oils, which can be processed excellently, for example, to colorless emulsions and smooth creams for cosmetic purposes.

OBJECTS OF THE INVENTION

It is the object of the present invention to make available new compounds for use in cosmetic products and a method for their production.

Another object of the present invention is the obtaining of a 1,3-dialkyl-cyclohexane having the formula: ##STR3## wherein R1 is a member selected from the group consisting of hydrogen and straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl.

A further object of the present invention is the development of a process for the production of the above 1,3-dialkyl-cyclohexane consisting essentially of the steps of hydrogenating a compound selected from the group consisting of:

(1) 2,6-dialkyl-cyclohexanone having the formula: ##STR4## and

(2) 2,6-dialkyl-cyclohexanol having the formula: ##STR5## wherein R1 is a member selected from the group consisting of hydrogen and straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl,

in the presence of a hydrogenation catalyst at a temperature of from 200 to 300 C. and a hydrogen pressure of between 10 and 300 bar, and recovering 1,3-dialkyl-cyclohexane.

A yet further object of the present invention is the obtaining of a cosmetic product having an effective amount of at least one 1,3-dialkyl-cyclohexane therein, together with the customary cosmetic adjuvants and auxiliaries.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION

The above objects have been achieved by the development of 1,3-dialkyl-cyclohexanes which can be represented by the following general Formula I: ##STR6## wherein R1 stands for hydrogen or a possibly branched C1 -C20 -alkyl and R2 for a possibly branched C1 -C20 -alkyl.

More particularly, the present invention relates to a 1,3-dialkyl-cyclohexane having the formula: ##STR7## wherein R1 is a member selected from the group consisting of hydrogen and straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl. Preferred are compounds in which R1 and R2, which may be identical or different, represent an alkyl, especially those compounds in which R1 and R2 stand for a C1 -C6 -alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl.

These compounds are prepared by a method according to the following reaction equation: ##STR8## wherein R1 and R2 have the above-mentioned meanings.

The process of the invention of preparing the 1,3-dialkyl-cyclohexane of Formula I consisting essentially of the steps of hydrogenating a compound selected from the group consisting of:

(1) 2,6-dialkyl-cyclohexanone having the formula: ##STR9## and

(2) 2,6-dialkyl-cyclohexanol having the formula: ##STR10## wherein R1 is a member selected from the group consisting of hydrogen and straight chained or branched C1 -C20 -alkyl and R2 is a straight chained or branched C1 -C20 -alkyl,

in the presence of a hydrogenation catalyst at a temperature of from 200 to 300 C. and a hydrogen pressure of between 10 and 300 bar, and recovering 1,3-dialkyl-cyclohexane.

As starting product for the production of 1,3-dialkyl-cyclohexanes of the invention, a cyclohexanone (II) or cyclohexanol (III) correspondingly substituted in the 2 and 6 positions with the desired alkyls is employed. Either are hydrogenated under hydrogenating conditions in the presence of a catalyst at elevated temperature and a hydrogen pressure of 10 to 300 bar for several hours, for example, 5 to 15 hours. All reaction steps are carried out without isolation of the respective intermediate products in the single pot method. Suitable hydrogenation catalysts are, for example, metallic nickel, cobalt, iron, or precious metals, such as platinum or palladium. Preferably the reaction is carried out with a nickel catalyst at temperatures of 200 to 300 C. The 2,6-dialkyl-cyclohexanol compounds used as starting products are obtained by mixed aldol condensation between 2 mols of aldehyde of the Formula V: ##STR11## wherein R1 and R2 have the above-mentioned meanings, and one mol of cyclohexanone and subsequent hydrogenation. Alternatively, the 2,6-dialkyl-cyclohexanol (III) compounds can be obtained from alcohol of the Formula VI: ##STR12## where R1 and R2 have the above-mentioned meaning, and cyclohexanol under the conditions of a mixed Guerbet alcohol reaction. This method for the production of 2,6-dialkyl-cyclohexanol has been described in Schaper, Fette, Seifen, Antrichmittel (1980), 82, pages 554-556.

The products according to the invention occur in the form of colorless oils. They are odorless and they are especially well suitable as cosmetic oils. They have refatting properties, and they are very well tolerated by the skin. The saturated, branched hydrocarbons used until now as an ointment base in cosmetic creams, such as Vaseline, cause heat accumulation on the skin surface as they clog the pores of the skin. This heat accumulation usually creates an unpleasant hot feeling. This undesired effect is avoided when using the compounds of the invention instead of the Vaseline. The compounds of the invention can be incorporated readily into various cosmetic preparations, such as suspensions, gels, emulsions, ointments, pastes, or shaking mixtures. Among the cosmetic products in which the compounds of the invention are usable are, for example, skin creams, body lotions, cleansing lotions, makeup bases, or sun protection agents.

In addition to the compounds according to the invention, the topical cosmetics may contain other components, such as preservatives, sequestering agents, perfumes, solvents, opacifiers, thickeners, dyes, pH-modifying additives, plant extracts, skin care ingredients, such as collagens, fatty acids, fatty acid esters, glycols, glycol ethers, animal, plant or synthetic oils and the like.

The compounds according to the invention are present in the cosmetics generally in quantities of 2% to 25% by weight, preferably 5% to 15% by weight, referred to the total weight of the cosmetic.

The following examples will further explain the present invention without being limitative in any manner. In the examples, all of the boiling points are indicated at the pressure measured in "mbars".

EXAMPLE 1 Production of 1,3-di-(2-ethylhexyl)-cyclohexane

300 Grams of 2,6-di(2-ethylhexyl)-cyclohexanol were hydrogenated with 30 gm of Girdler nickel 49A for six hours at 250 C. and 250 bar of hydrogen pressure. After filtration of the catalyst, 260 gm of 1,3-di-(2-ethylhexyl)-cyclohexane remained with the following characteristics:

______________________________________Acid number:      0.1Hydroxyl number:  0Iodine number:    0Molar mass:       308 (theory 308)IR (oil) cm-1 :             2965, 2930, 2880, 2865,             1460, 1380.______________________________________
EXAMPLE 2 Production of 1,3-di-(2-ethylhexyl)-cyclohexane

200 Grams of 2,6-di-(2-ethylhexyl)-cyclohexanol were hydrogenated for 13 hours at 250 C. and 20 bar of hydrogen pressure with 10 gm of a nickel catalyst containing about 22% nickel bonded on kieselguhr in a hard fat (Pricat 9904 of Unichema). After filtration of the catalyst, 171 gm of 1,3-di-(2-ethylhexyl)-cyclohexane were obtained after distillation at 0.01 mbar between 118 and 123 C.

______________________________________Characteristics:______________________________________Acid number:      0.2Hydroxyl number:  1.5Iodine number:    1.4IR (oil) cm-1 :             2965, 2930, 2880, 2865,             1460, 1380.______________________________________
EXAMPLE 3

The same reaction of Example 2 was repeated with 20 gm of Pricat catalyst. After 15 hours hydrogenation time, 160 gm of 1,3-di-(2-ethylhexyl)-cyclohexane were obtained having the following characteristics:

______________________________________Acid number:           0.1Hydroxyl number        0Iodine number          0.4B.P.0.013 :       127 C.______________________________________
EXAMPLE 4 Production of 1,3-diisobutyl-cyclohexane

85 Grams of 2,6-diisobutyl-cyclohexanol were hydrogenated with 8.5 gm of Girdler nickel 49A for eight hours at 250 C. and 250 bar of hydrogen pressure. After filtration of the catalyst, 61 gm of the hydrocarbon 1,3-diisobutyl-cyclohexane were isolated by distillation.

______________________________________Characteristics:______________________________________Acid number:      0.1Hydroxyl number   0Molar number:     196Theory:           196B.P.0.07 :   51 C.IR (oil) cm-1 :             2960, 2930, 2865, 2845,             1470, 1385, 1370, 1170.______________________________________
EXAMPLE 5 1,3-Di-(2-ethylbutyl)-cyclohexane

As described in Example 4, starting from 94 gm of 2,6-di-(2-ethylbutyl)-cyclohexanol, 62 gm of the hydrocarbon 1,3-di-(2-ethylbutyl)-cyclohexane were produced with 9.4 gm of Girdler nickel 49A.

______________________________________Characteristics:______________________________________Acid number:      0Hydroxyl number:  0.5Molar mass:       252Theory:           252B.P.0.01 93 to 95 C.IR (oil) cm-1 :             2960, 2920, 2865, 2860             1460, 1380.______________________________________
EXAMPLE 6 1,3-(Di-(2-methylpentyl)-cyclohexane

As described in Example 4, starting from 100 gm of 2,6-di-(2-methylpentyl)-cyclohexanol, 75 gm of the hydrocarbon 1,3-di-(2-methylpentyl)-cyclohexane were produced with 10 gm of Girdler nickel 49A.

______________________________________Characteristics:______________________________________Acid number:      0Hydroxyl number:  0Molar mass:       252Theory            252B.P.0.01 :   88 to 91 C.IR (oil) cm-1 :             2965, 2930, 2870, 2850,             1468, 1455, 1380, 1155.______________________________________
EXAMPLE 7 1,3-Didecyl-cyclohexane

137 Grams of 2,6-didecyl-cyclohexanol were hydrogenated with 14 gm of Girdler nickel 49A. 71 Grams of the hydrocarbon 1,3-didecyl-cyclohexane were recovered.

______________________________________Characteristics:______________________________________Acid number:      0Hydroxyl number:  0Molar mass:       364Theory:           364B.P.0.01 :   174 to 180 C.IR (oil) cm-1 :             2965, 2925, 2860, 1468,             1460, 1380.______________________________________

In the following, examples for cosmetic products according to the invention are given. The oils and oil-soluble components (I) were heated to 70 to 80 C. and mixed with the aqueous phase (II) which was also heated to 70 C. by stirring. Depending on the solubility, the preservative was previously dissolved in one of the two phases. The mixture was then cooled to room temperature with constant agitation.

EXAMPLE 8 Liquid Oil in Water (O/W) Emulsion

______________________________________(I)    Lanette O (C12-18 fatty alcohol)                       3.5%  Eumulgin B1 (cetyl/stearyl alcohol                       3.0%  adducted with about 12 mols of  ethylene oxide  1,3-Di-(2-ethylhexyl)-cyclohexane                       5.0%(II)   1,2-Propylene glycol 3.0%  Urea                 2.0%  Water                83.5%______________________________________
EXAMPLE 9 Oil in Water (O/W) Cream

______________________________________(I)    Eumulgin B3 (C12-18 fatty alcohol                       13.0%  adducted with about 30 mols of  ethylene oxide  Cetiol HE (a C12-18 fatty acid                       20.0%  ester with polyols  1,3-Di-(2-ethylhexyl)-cyclohexane                        5.0%(II)   Glycerol 86%         20.0%  Water                42.0%______________________________________
EXAMPLE 10 Oil in Water (O/W) Hair Styling Cream

______________________________________(I)  Eumulgin B1                 5.0%Cutina MD (palmitic/stearic acid mono- and di-                           15.0%glyceride)1,3-Di-(2-ethylhexyl)-cyclohexane                           20.0%(II) Water                      60.0%______________________________________
EXAMPLE 11 Oil in Water (O/W) Cleansing Cream

______________________________________(I)  Lanette 16 (cetyl alcohol)  2.0%Cutina MD (mixture of mono- and di-                            14.0%glycerides of palmitic andstearic acid)Eumulgin B1 (cetylstearylalcohol adduc-                            1.5%ted with about 12 mols of ethylene oxide)Eumulgin B2 (C16-18 - fatty alcohol                            1.5%adducted with about 20 mols ofethylene oxide)Cetiol LC (a caprylic/capric                            7.0%fatty acid ester with saturated C12-18 fatty alcohols1,3-Di-(2-ethylhexyl)-cyclohexane                            15.0%(II) Water                       59.0%______________________________________
EXAMPLE 12 Water in Oil (W/O) Cream

______________________________________(I)    Dehymuls K (mixture of Dehymuls E and                          25.0%  fatty alcohol fatty acid  esters and mineral fats)  Myritol 318 (lower boiling fatty                          10.0%  acid glycerides)  1,3-Di-(2-ethylhexyl)-cyclohexane                           5.0%(II)   Water                   60.0%______________________________________
EXAMPLE 13 (W/O) Cream

______________________________________(I)    Dehymuls E (mixture of higher molecular                          8.0%  esters, pref. pentaerithrit  fatty acid ester and fatty  alcohol citrate)  Vaseline, white         15.0%  1,3-Di-(2-ethylhexyl)-cyclohexane                          8.0%(II)   Glycerol 87%            3.0%  MgSO4.7H2 O   0.3%  Water                   65.7%______________________________________
EXAMPLE 14 (W/O) Cream

______________________________________(I)    Dehymuls E (mixture of higher molecular                          7.0%  esters, pref. pentaerithrit  fatty acid ester and fatty alcohol  citrate)  Cetiol V (decyl oleate) 6.0%  Beeswax, white          3.0%  Vaseline, white         12.0%  1,3-Diisobutyl-cyclohexane                          6.0%(II)   Glycerol 86%            5.0%  MgSO4 7H2 O   0.3%  Water                   60.7%______________________________________

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art or disclosed herein may be employed without departing from the spirit of the invention or the scope of the appended claims.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3748231 *Jan 27, 1972Jul 24, 1973Sun Research DevelopmentMicrobiological oxidation of alkyl-substituted cyclic compounds
US4190561 *Nov 10, 1976Feb 26, 1980Societe Anonyme Roure Bertrand DupontEsters of cyclohexene, odoriferous compositions containing said esters and process for the preparation thereof
US4206090 *Oct 6, 1978Jun 3, 1980International Flavors & Fragrances Inc.3-Methyl-1-phenyl-pentanol-5 or its isomer and butanoyl cyclohexane derivatives
Non-Patent Citations
Reference
1 *Chem. Abs., 1967, vol. 66, p. 54730y, Mekhtien et al.
2 *Chem. Abs., 8th Coll. Index, p. 9042s.
3 *Chem. Abs., vol. 68, 1968, p. 1182, Babakhanov et al.
4 *Chemical Abstracts Service Registry Handbook (1975 Supplement) Houben-Weyl Reference (p. 273) (1970).
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4784843 *Feb 20, 1986Nov 15, 1988Basf AktiengesellschaftDicyclohexylalkanes, their preparation, cosmetic and pharmaceutical formulations containing these compounds, and their use as oil components
US4847073 *Jun 29, 1988Jul 11, 1989Ici Americas Inc.Ultraviolet radiation absorbing cyclohexenylidene method
US5000950 *May 28, 1986Mar 19, 1991Smith & Nephew Medical Ltd.Agent for the treatment of wounds
US6432419 *Jun 3, 1997Aug 13, 2002Cognis Deutschland GmbhUse of fats to replace silicone in cosmetic and/or pharmaceutical preparations
US7365235Sep 11, 2001Apr 29, 2008Cognis Deutschland Gmbh & Co. KgProcesses for producing branched compounds via condensation and hydrogenation
US7501546Dec 11, 2006Mar 10, 2009Neste Oil OjProcess for producing a branched hydrocarbon component
US7850841Dec 12, 2006Dec 14, 2010Neste Oil OyjProcess for producing a branched hydrocarbon base oil from a feedstock containing aldehyde and/or ketone
US7888542Dec 12, 2006Feb 15, 2011Neste Oil OyjProcess for producing a saturated hydrocarbon component
US7967973Apr 30, 2009Jun 28, 2011Neste Oil OyjProcess for producing a hydrocarbon component
US7998339Dec 11, 2006Aug 16, 2011Neste Oil OyjProcess for producing a hydrocarbon component
US8053614Dec 12, 2006Nov 8, 2011Neste Oil OyjBase oil
US8394258Nov 24, 2010Mar 12, 2013Neste Oil OyjProcess for producing a hydrocarbon component
US8715486Feb 1, 2013May 6, 2014Neste Oil OyjProcess for producing a hydrocarbon component
US20030181769 *Sep 11, 2001Sep 25, 2003Sabine BothMethod for producing branched alcohols and/or hydrocarbons
US20070131579 *Dec 12, 2006Jun 14, 2007Neste Oil OyjProcess for producing a saturated hydrocarbon component
US20070135316 *Dec 12, 2006Jun 14, 2007Neste Oil OyjProcess for producing a branched hydrocarbon component
US20070135666 *Dec 11, 2006Jun 14, 2007Neste Oil OyjProcess for producing a branched hydrocarbon component
US20070161832 *Dec 11, 2006Jul 12, 2007Neste Oil OyjProcess for producing a hydrocarbon component
US20090247799 *Apr 30, 2009Oct 1, 2009Jukka MyllyojaProcess for producing a hydrocarbon component
US20110105814 *Nov 24, 2010May 5, 2011Neste Oil OyjProcess for producing a hydrocarbon component
EP2666819A2 *Jan 18, 2012Nov 27, 2013Hanwha Chemical CorporationVinyl chloride resin composition comprising diethylhexylcyclohexane for wallpaper
EP2666819A4 *Jan 18, 2012Aug 6, 2014Hanwha Chemical CorpVinyl chloride resin composition comprising diethylhexylcyclohexane for wallpaper
Classifications
U.S. Classification514/763, 424/59, 424/63, 585/20
International ClassificationA61K8/30, C07C67/00, C07C13/16, C07C1/22, C07C1/00, C07C13/18, A61K8/31, C07C5/02, A61Q5/06, A61Q19/00, A61Q19/10
Cooperative ClassificationA61K8/31, C07C2523/75, C07C2523/42, C07C2523/745, A61Q19/00, C07C2523/44, C07C2523/755, C07C1/22, C07C13/18, A61Q5/06, C07C2601/14
European ClassificationC07C1/22, A61Q19/00, A61K8/31, C07C13/18
Legal Events
DateCodeEventDescription
Apr 23, 1984ASAssignment
Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN (HENKEL KG
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CONRAD, JENS;SCHAPER, ULF-ARMIN;ZEIDLER, ULRICH;REEL/FRAME:004247/0151
Effective date: 19811211
Jan 4, 1988FPAYFee payment
Year of fee payment: 4
Jan 3, 1992FPAYFee payment
Year of fee payment: 8
Jan 3, 1996FPAYFee payment
Year of fee payment: 12
Feb 6, 1996REMIMaintenance fee reminder mailed